Colorant compositions

ABSTRACT

Disclosed is a colorant composition of the formula 
                         
wherein R is an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group, and wherein R can be joined to the phenyl moiety to form a ring, R′ is an aromatic- or heteroaromatic-containing group, each R a , independently of the others, is a halogen atom, an alkyl group, an alkoxy group, a nitrile group, a nitro group, an amide group, or a sulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integer representing the number of carbon atoms in each repeat alkylene oxide unit, and x is an integer representing the number of repeat alkylene oxide units, wherein said colorant has no more than one —OH, —SH, or primary or secondary amino group per molecule.

This application is a divisional of U.S. application Ser. No.10/854,580, filed May 25, 2004, now U.S. Pat. No. 6,969,759, which is adivisional of U.S. application Ser. No. 10/422,742, filed Apr. 24, 2003,now U.S. Pat. No. 6,764,541, the disclosures of each of which aretotally incorporated herein by reference.

CROSS-REFERENCES TO COPENDING APPLICATIONS

Copending application U.S. Ser. No. 10/422,755, filed Apr. 24, 2003, nowU.S. Pat. No. 7,034,185, entitled “Colorant Precursor Compositions,”with the named inventors Jeffery H. Banning, Donald R. Titterington, andClifford R. King, the disclosure of which is totally incorporated hereinby reference, discloses colorant precursor compounds of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, each R′, independently of the others, is a halogen atom, analkyl group, an alkoxy group, a nitrile group, a nitro group, an amidegroup, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n isan integer representing the number of carbon atoms in each repeatalkylene oxide unit, and x is an integer representing the number ofrepeat alkylene oxide units, wherein said colorant precursor has no morethan one —OH, —SH, or primary or secondary amino group per molecule.

Copending application U.S. Ser. No. 10/422,897, filed Apr. 24, 2003, nowU.S. Pat. No. 6,790,267, entitled “Colorant Compositions,” with thenamed inventors Jeffery H. Banning, Donald R. Titterington, and CliffordR. King, the disclosure of which is totally incorporated herein byreference, discloses colorant compounds of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, each R¹, independently of the others, is a halogen atom, analkyl group, an alkoxy group, a nitrile group, a nitro group, an amidegroup, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n isan integer representing the number of carbon atoms in each repeatalkylene oxide unit, x is an integer representing the number of repeatalkylene oxide units, and A and B each, independently of the other, arehydrogen atoms, halogen atoms, tertiary amino groups, imine groups,ammonium groups, cyano groups, pyridine groups, pyridinium groups, ethergroups, ester groups, amide groups, sulfate groups, sulfonate groups,sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, sulfonegroups, acyl groups, azo groups, cyanato groups, alkyl groups, alkoxygroups, aryl groups, aryloxy groups, arylalkyl groups, arylalkyloxygroups, alkylaryl groups, or alkylaryloxy groups, wherein said coloranthas no more than one —OH, —SH, or primary or secondary amino group permolecule.

Copending application U.S. Ser. No. 10/422,895, filed Apr. 24, 2003,U.S. Publication 20040214918, entitled “Colorant Compositions,” with thenamed inventors Jeffery H. Banning, Donald R. Titterington, and CliffordR. King, the disclosure of which is totally incorporated herein byreference, discloses colorant compounds of the formula

wherein R, R₁, R₂, R₃, and R₄ each, independently of the others, is analkyl group, an aryl group, an arylalkyl group, or an alkylaryl group,and wherein R, R₁, R₂, R₃, and R₄ each can be joined to a phenyl moietyto form a ring, each R′_(a), R′_(b), and R′_(c), independently of theothers, is a halogen atom, an alkyl group, an alkoxy group, a nitrilegroup, a nitro group, an amide group, or a sulfonamide group, z1, z2,and z3 each, independently of the others, is an integer of 0, 1, 2, 3,or 4, n is an integer representing the number of carbon atoms in eachrepeat alkylene oxide unit, x is an integer representing the number ofrepeat alkylene oxide units, D is an anion, and g is the charge on theanion, wherein said colorant has no more than one —OH, —SH, or primaryor secondary amino group per molecule.

BACKGROUND OF THE INVENTION

The present invention is directed to specific colorant compounds and toink compositions containing these colorant compounds. More specifically,the present invention is directed to specific reactive azo colorantcompounds and to ink compositions containing these colorant compounds.One embodiment of the present invention is directed to a colorantcomposition of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R¹ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said colorant has no more than one —OH, —SH, orprimary or secondary amino group per molecule. Another embodiment of thepresent invention is directed to a compound comprising two or moremoieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said moieties each contain no —OH groups, —SHgroups, or primary or secondary amino groups, said moieties being linkedby a central atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change ink carrier and a colorant compound comprisingone or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 5,864,002 (Stephens et al.), the disclosure of which istotally incorporated herein by reference, discloses a method ofproviding for manufacturing a colored polymer resin having the steps of:(a) blending a disazo colorant into a mixture of monomers, the coloranthaving a poly(oxyalkylene) substituent comprising from 2 to 200 alkyleneoxide residues, bonded to each end of the disazo chromophore, thepoly(oxyalkylene) substituent having a nucleophilic terminal group whichis capable of reacting with at least a portion of the monomers; (b)providing conditions under which the monomers and disazo colorantpolymerize to form a colored polymer resin.

U.S. Pat. No. 5,591,833 (Hines et al.), the disclosure of which istotally incorporated herein by reference, discloses colorants andcompositions useful as a fugitive or permanent colorant for a variety ofsubstrates, or as intermediates for their manufacture, and having one ormore improved properties of enhanced aqueous washability, compatibilitywith and non-extractibility from thermoplastic resins, or reactivitywith resins having reactive functionality, said composition having theformula C(Z)₁₋₈ wherein C is the residue of a reactant having from 1 to8 nucleophilic site residues to which the Z moieties are attached; saidZ moieties containing at least about 60 weight percent ofpoly(oxyalkylene) which comprises (a) at least one glycidol residuesegment of 2 to 6 glycidol residues attached to a nucleophilic site ofC, wherein said poly(oxyalkylene) contains a total of from 2 to 20glycidol residues, (b) and wherein said poly(oxyalkylene) furthercontains the residues of one or more other epoxide reactants of ethyleneoxide (EO), propylene oxide (PO), or butylene oxide (BO), or mixturesthereof, wherein said poly(oxyalkylene) contains a total of from about10 to about 600 of said EO, PO, or BO residues, or mixtures thereof, atleast about 75 mole percent of which are EO residues, (c) and with theprovisions that the ratio of the total of —O—PO— and —O—BO— linkages ofall glycidol residues to the total of all functional oxy linkages ofsaid glycidol residues is less than one, and the molar ratio of EOresidues to glycidol residues is from 4 to 75.

U.S. Pat. No. 5,290,921 (Moody et al.), the disclosure of which istotally incorporated herein by reference, discloses primary hydroxylenhanced colorants having markedly improved reactivities in e.g.,polyurethane foams for imparting permanent coloring thereto, thecolorants having the formula C—(Z)¹⁻⁴ wherein C is an azo, methine, orazamethine chromogen and Z is a poly(oxyalkylene) moiety comprising (1)at least two (A) units independently selected from those of the formulae—CH₂CH(O—T)CH₂O— or —CH₂CH(O—T)CH₂O—T and (2) from none to about 200 (B)units of the formula (—RO—) wherein R is straight or branched chainhydrocarbon of 2 to 4 carbons, T is a moiety of the formula—CH₂CH(R₁)—O—(RO)₀₋₄₀—CH₂CH₂OH wherein R₁ is selected from unsubstitutedor substituted alkyl, aryl, alkenyloxyalkyl, alkoxyalkyl, oraryloxyalkyl, and wherein the A units comprise at least 0.5 percent ofthe total A+B units.

U.S. Pat. No. 5,108,460 (Hines et al.), the disclosure of which istotally incorporated herein by reference, discloses azo chromophoreshaving polyoxyalkylene substituents that are linked together by acovalent bond or by an intervening connecting group to form dimers ortrimers. The polyoxyalkylene substituents are straight or branched chainpolymers primarily of ethylene oxide which make the dimer and trimercolorants useful as fugitive tints.

U.S. Pat. No. 5,082,938 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses enhanced branchedchain hydroxyl compounds of formula Y—(Z)₁₋₆ wherein Y is the residue ofa nucleophile devoid of conjugated divalent linking moieties, and each Zis a poly(oxyalkylene) moiety having a molecular weight of from about200 to 10,000 and containing at least one glycidol residue, wherein atleast one of the primary oxy sites of said glycidol residue is linkedpreferably directly to a first epoxide residue of three or more carbons,and wherein said first epoxide residue is linked through a secondary oxysite preferably directly to a second epoxide reside having a primaryterminal hydroxyl.

U.S. Pat. No. 5,043,013 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a washable aqueousink composition having a viscosity of from about 1.0 to about 6.0centipoise and containing from about 10 to about 50 percent by weight ofone or more polymeric colorants of the formula{R₁[(RO)_(a)—Y]_(b)}_(c)wherein X is a polar group such as sulfonic acids, sulfonic acid salts,sulfonamides, sulfonates or the like: R is alkylene; Y is H, alkanoyl,carbamoyl, or the like; R, is nitrogen, oxygen, sulfur, or asulfur-containing divalent linking group; a is an integer of from six toabout forty; b and c are each independently selected from one or two; dis an integer of from one to four; the product of (a) (b) (c) is aninteger of from 6 to about 40; and CHROM is a chromophore such as nitro,nitroso, monoazo, disazo and trisazo, diarylmethane, triarylmethane,xanthane, acridine, methine, thiazole, indamine, azine, oxazine, oranthraquinone, wherein the (RO)_(a) moiety is bonded to a carbocyclicaromatic ring of the (CHROM) through R₁.

U.S. Pat. No. 4,751,254 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring polyurethane resins during the production of same with reactivecolorants derived from polyalkoxytrifluoroaniline intermediates. Thesecolorants impart increased brightness in shade for both aromatic andheteroaromatic derivatives and increased resistance to stannousoctanoate catalyst over conventional polymeric colorants derived forheteroaromatic compounds. These colorants have the structure

wherein R₁ is selected from H, a lower alkyl group containing from 1 toabout 10 carbon atoms, CH₂Cl, CH₂OH, phenyl, or

where R₆ is H or a lower alkyl group containing from 1 to about 9 carbonatoms; R₂ is selected from OH, NH₂, or SH; R₃ is selected from a loweralkyl group containing from 1 to about 9 carbon atoms, cyanoalkyl,acetoxyalkyl, or

where R₁ and R₂ are as given above; R₄ is H, CF₃, a lower alkyl groupcontaining from 1 to about 9 carbon atoms, Cl, or Br and n is 0 or aninteger from 1 to about 125. R₅ is an aromatic or heteroaromaticcontaining group, said colorants being resistant to stannous octanoate,being characterized as having improved brightness and which havefunctionality through reactive substituents thereof.

U.S. Pat. No. 4,658,064 (Moore et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound of theformula

wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ is selectedfrom H or alkyl; Y is a number of from 2 to about 200; and Z is selectedfrom H or

where W is alkyl.

U.S. Pat. No. 4,594,454 (Moore et al.), the disclosure of which istotally incorporated herein by reference, discloses a compound of theformula

wherein R₁ is selected from alkyl, halide, or alkoxy; R₂ is selectedfrom H or alkyl; Y is a number of from 2 to about 200; and Z is selectedfrom H or

where W is alkyl.

U.S. Pat. No. 4,400,320 (Keller et al.), the disclosure of which istotally incorporated herein by reference, discloses fugitive tints whichare characterized by the formula

where R is selected from meta-toluidene, meta-amino phenol, aniline, ordimethoxy aniline, A is selected from N, O, S, or CO₂; the alkylenegroup of the alkyleneoxy constituent contains from 2 to about 4 carbonatoms; n is an integer of from 2 to about 300; m is 1 when A is O, S, orCO₂, and 2 when A is N; x is an integer of from 1 to about 5; and theproduct of n times m times x (n·m·x) is from 2 to about 400. Alsodisclosed is a process for preparing alkyleneoxy fugitive tints.

U.S. Pat. No. 4,284,729 (Cross et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring thermosetting resins, made by polyaddition reaction of anucleophile with an electrophile, with a polymeric liquid reactivecoloring agent suitable for incorporation in the resin with theformation of covalent bonds, said coloring agent having the formulaR-(polymeric constituent-X)_(n)wherein R is an organic dyestuff radical; the polymeric constituent isselected from polyalkylene oxides and copolymers of polyalkylene oxidesin which the alkylene moiety of the polymeric constituent contains 2 ormore carbon atoms and such polymeric constituent has a molecular weightof from about 44 to about 1500; and n is an integer of from 1 to about6; and X is selected from —OH, —NH₂, and —SH, said coloring agent beingadded in an amount sufficient to provide coloration of saidthermosetting resin.

U.S. Pat. No. 4,132,840 (Hugl et al.), the disclosure of which istotally incorporated herein by reference, discloses polyurethaneplastics that are dyed with dyestuffs of the formula

wherein R₁ denotes hydrogen, halogen, optionally substituted C₁-C₄alkyl, optionally substituted C₁-C₄ alkoxy, and optionally substitutedC₁-C₄ alkylcarbonylamino and R₂ denotes hydrogen, optionally substitutedC₁-C₄ alkyl, and optionally substituted C₁-C₄ alkoxy, while A and Bdenote optionally branched alkylene chains which can be identical ordifferent and preferably have 2 to 6 carbon atoms, with formation ofcovalent bonds, in that the dyestuffs are added before or during thepolyaddition reaction to the reaction mixture of polyol andpolyisocyanate or to one of the components.

U.S. Pat. No. 3,994,835 (Wolf et al.), the disclosure of which istotally incorporated herein by reference, discloses dispersions ofdyestuffs which contain at least one free amino or hydroxyl groupcapable of reacting with isocyanates under the conditions ofpolyaddition and liquids in which the dyes are soluble to an extent lessthan 2 percent which are suitable for the production of coloredpolyurethane foams. The dye dispersions can be added before or duringthe polyaddition reaction.

U.S. Pat. No. 5,270,363 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a colorant fornatural or synthetic resinous or polymeric materials, having the formulaA-[SO₂—N(R₂)—Y]₁₋₄ wherein R₂ is selected for example from hydrogen,methyl, cyclohexyl, phenyl or Y; A is a nonionic metallophthalocyaninechromophore which can be substituted for example with halogen, alkyl,alkoxy, alkylthio, or aryloxy, Y is a poly(oxyalkylene) moietycontaining at least three monomeric units or mixtures thereof of theformula (—RO—) wherein each R is straight or branched alkylene of 1 to 4carbons or mixtures thereof, up to about 20 mole percent of saidmonomeric units may be connected by one or more linking groups such asalkyleneoxy, —NH—, or —NHCONH—, and wherein Y can be terminated byhydrogen, or by at branch substituents, containing 1 to 3 groups ormoieties selected from alkyl, cycloalkyl, acyl, or aryl; wherein any ofthe above recited hydrocarbon groups, moieties or substituents maythemselves be substituted with up to four substituents selected, forexample, from alkyl, halogen, mercapto, alkoxycarbonyl, hydroxy, alkoxy,or the like; and wherein each aliphatic hydrocarbon portion or moiety ofthe groups, moieties or substituents recited above contains from 1 to 20carbons.

U.S. Pat. No. 4,912,203 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses thiophene basedcolorants useful for coloring thermoset resins such as polyurethanesbeing of the formula

wherein R₁, R₂, and R₃ are selected from halogen, carboxylic acid,alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl,aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl, thiocyano,carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl, amidoaryl,amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl, or hydrogenwhen an adjacent group is isobutyryl; R₄, R₅, and R₇ are selected fromhydrogen alkyl, oxyalkyl, sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl,amidodialkyl, amidoaryl, amidodiaryl, halogen, thioalkyl, and thioaryl;and R₈ and R₉ are selected from polyalkylene oxide, copolymers ofpolyalkylene oxides, and hydroxyalkylenes.

U.S. Pat. No. 4,846,846 (Rekers et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forcoloring polyurethane resins made by a polyaddition reaction of a polyoland an isocyanate which comprises adding to the reaction mixture beforeor during the polyaddition reaction a reactive coloring agent suitablefor incorporation in the resin with the formation of covalent bonds,said coloring agent having the formula

in which R₁ and R₂ are independently selected from an alkyl group havingfrom 1 to about 12 carbon atoms, X is —CH₂—, a and a′ are integers from1 to about 6, and Y and Y′ are independently selected from polymericunits of hydroxy alkylenes or alkylene oxide monomers selected fromethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, orglycidol, b and b′ are independently either 0 or 1, and Z and Z′ arereactive groups independently selected from —OH, —NH₂, or —SH.

U.S. Pat. No. 4,507,407 (Kluger et al.), the disclosure of which istotally incorporated herein by reference, discloses a process ofcoloring polyurethane resins during the production of same with reactivecolorants having the formula

wherein R₁, R₂, R₃ are selected from halogen, carboxylic acid, alkanoyl,aryloyl, alkyl, aryl, cyano, sulfonylalkyl, sulfonylaryl, thioalkyl,thioaryl, sulfinylalkyl, sulfinylaryl, dithioalkyl, dithioaryl,thiocyano, amidoalkyl, amidodialkyl, oxyalkyl, oxyaryl, hydrogen,sulfonamidoalkyl, sulfonamidoaryl, sulfonamidodialkyl,sulfonamidodiaryl, carbocyclic forming polymethylene chains,sulfenamidoalkyl, sulfenamidodialkyl, sulfenamidoaryl,sulfenamidodiaryl, sulfinamidoalkyl, sulfinamidodialkyl,sulfinamidoaryl, sulfinamidodiaryl, and A is an organic dyestuff couplerthat is resistant to stannous octanoate and flame retardant compoundsand which has functionality through reactive substituents thereof.

U.S. Pat. No. 5,919,839 (Titterington et al.), the disclosure of whichis totally incorporated herein by reference, discloses colored waxesmade by reacting selected nucleophiles, including alcohol containingcolorants, with an isocyanate. A phase change ink is made by blendingthe colored wax with a clear ink carrier composition. The clear inkcarrier composition can be a fatty amide-based material and/or acombination of isocyanate-derived resins in which the order of additionof the isocyanate and the different nucleophiles can tailor thedistribution of di-urethane, mixed urethane/urea, and/or di-ureamolecules in the final resin product. The colored wax materials areuseful as ingredients with phase change ink carrier compositions to makephase change ink jet inks.

U.S. Pat. No. 5,456,725 (Bruhnke), the disclosure of which is totallyincorporated herein by reference, discloses a process for temporarilycoloring a polyamide substrate whereby a poly(oxyalkylene) substitutedmethine colorant is applied to the substrate followed by heating thesubstrate with superheated steam at a temperature of 250° F. or greater,which effectively decolorizes the methine colorant.

PCT Patent Application WO 97/13816, the disclosure of which is totallyincorporated herein by reference, discloses a colored material suitablefor use in a hot melt ink comprising a oligomeric hot melt ink jetvehicle formed of molecules having a backbone and at least one pendantside-chain. A dyestuff is reacted onto the backbone. The material ispreferably obtainable as the reaction product of an aliphatic oraromatic mono- or di-isocyanate and a hydroxyl group functional dyecomponent, and optionally one or more other suitable material. Suchsuitable materials include mono- and dihydric alcohols, primary andsecondary monoamines, functional amides, hydroxyl functional amines andhydroxyl containing components having a terminal unsaturated bond.

“Polymeric Colorants,” J. Miley, IUPAC Pure and Applied Chemistry, Vol.68, No. 7, p. 1423 (1996), the disclosure of which is totallyincorporated herein by reference, discloses specific examples ofpolymeric colorants and how they meet functional requirements.

While known compositions are suitable for their intended purposes, aneed remains for improved reactive azo colorants. In addition, a needremains for reactive azo colorants that are easily purified. Further, aneed remains for reactive azo colorants that exhibit reduced toxicity.Additionally, a need remains for reactive azo colorants that are liquidat room temperature. There is also a need for reactive azo colorantsthat can be tailored for compatibility with various hydrophobic orhydrophilic applications. In addition, there is a need for reactive azocolorants that, when reacted with or reacted to form oligomers orpolymers such as polyurethanes, polyanhydrides, or the like, resistmigration and/or settling. Further, there is a need for reactive azocolorants that, when reacted with other materials, do not result in theformation of products of undesirably high molecular weight.Additionally, there is a need for reactive azo colorants that, whenreacted with other materials, do not result in the formation of productswith undesirable crosslinking. A need also remains for reactive azocolorants that, when reacted with other materials, form productssuitable for use in phase change ink compositions. In addition, a needremains for reactive azo colorants that, when reacted with othermaterials, form products that, when incorporated into phase change inkcompositions, exhibit reduced precipitation of the colorant from theink. Further, a need remains for reactive azo colorants that, whenreacted with other materials, form products that, when incorporated intophase change ink compositions, exhibit reduced clogging of printer headsand resulting printer failure.

SUMMARY OF THE INVENTION

The present invention is directed to a colorant composition of theformula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said colorant has no more than one —OH, —SH, orprimary or secondary amino group per molecule. Another embodiment of thepresent invention is directed to a compound comprising two or moremoieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said moieties each contain no —OH groups, —SHgroups, or primary or secondary amino groups, said moieties being linkedby a central atom or group of atoms or bonded to a polymer. Yet anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change ink carrier and a colorant compound comprisingone or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

DETAILED DESCRIPTION

The present invention is directed to a colorant of the formula

wherein R is an alkyl group (including linear, branched, saturated,unsaturated, cyclic, and unsubstituted alkyl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in another embodiment withat least about 2 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including unsubstituted and substitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 5 carbon atoms,and in another embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 6 carbon atoms, and in another embodiment with atleast about 7 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl group (including unsubstituted andsubstituted alkylaryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the alkylaryl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges,wherein the substituents on the substituted alkyl, aryl, arylalkyl, andalkylaryl groups can be (but are not limited to) halogen atoms, tertiaryamino groups, imine groups, ammonium groups, cyano groups, pyridinegroups, pyridinium groups, ether groups, ester groups, amide groups,sulfate groups, sulfonate groups, sulfide groups, sulfoxide groups,phosphine groups, phosphonium groups, phosphate groups, nitrile groups,mercapto groups, nitro groups, sulfone groups, acyl groups, azo groups,cyanato groups, and the like, as well as mixtures thereof, and whereintwo or more substituents can be joined together to form a ring, R′ is anaromatic- or heteroaromatic-containing group, each R_(a), independentlyof the others, is a halogen atom, an alkyl group, an alkoxy group, anitrile group, a nitro group, an amide group, or a sulfonamide group, wis an integer of 0, 1, 2, 3, or 4, n is an integer representing thenumber of carbon atoms in each repeat alkylene oxide unit (the alkyleneoxide units can each have different numbers of carbon atoms; forexample, the polyalkylene oxide chain can comprise a mixture of repeatethylene oxide, propylene oxide, and/or butylene oxide units), and inone embodiment is at least about 2, and in one embodiment is no morethan about 18, and in another embodiment is no more than about 4,although the value of n can be outside of these ranges, and x is aninteger representing the number of repeat alkylene oxide units, and inone embodiment is at least about 2, and in another embodiment is atleast about 5, and in one embodiment is no more than about 100, and inanother embodiment is no more than about 20, although the value of x canbe outside of these ranges, wherein said colorant has no more than one—OH, —SH, or —NHR_(b) group (i.e., primary or secondary amino group) permolecule, wherein R_(b) is a hydrogen atom, an alkyl group (includinglinear, branched, saturated, unsaturated, cyclic, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least 1 carbonatom, and in another embodiment with at least about 2 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, and inanother embodiment with no more than about 48 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(including unsubstituted and substituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least 5 carbon atoms, and in another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about48 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group.

If desired, various substituents (shown as R_(a) groups on thestructure) can be present on the central phenyl moiety of the structureto affect the color of the colorant. From 1 to 4 of such substituentscan be present, which can be the same as each other or different fromeach other. Examples of such substituents include (but are not limitedto) halogen atoms, such as fluorine, chlorine, bromine, and iodine,alkyl groups, in one embodiment with at least 1 carbon atom, and in oneembodiment with no more than about 25 carbon atoms, such as methyl,ethyl, and the like, alkoxy groups, in one embodiment with at least 1carbon atom, and in one embodiment with no more than about 25 carbonatoms, such as methoxy groups, ethoxy groups, and the like, nitrilegroups, nitro groups, amide groups, such as an acetamido group or thelike, including (but not limited to) those of the general formula

wherein R_(m) is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, and in another embodiment with no more than about 48carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, such as anacetamido group or the like, sulfonamide groups, including (but notlimited to) those of the formula

wherein R_(p) is a hydrogen atom, an alkyl group (including linear,branched, saturated, unsaturated, cyclic, and unsubstituted alkylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe alkyl group), in one embodiment with at least 1 carbon atom, and inanother embodiment with at least about 2 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 48 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 50carbon atoms, and in another embodiment with no more than about 48carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms,and in another embodiment with no more than about 48 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 6 carbon atoms, and in another embodiment with at least about 7carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 48 carbonatoms, although the number of carbon atoms can be outside of theseranges, such as tolyl or the like, and wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) those indicated hereinabove for the R group, or thelike.

It should be noted that the R group can also be joined to the centralphenyl moiety to form a ring; for example, compounds of the formulae

are within the scope of the above formula.

The colorants of the present invention can be prepared by, for example,reacting an N-alkyl aniline with suitable reactants to form a materialof the formula

wherein R, R_(a), w, n, and x are as defined hereinabove. Morespecifically, the corresponding N-alkyl aniline can be reacted with anepoxide compound containing the desired number of carbon atoms in thepresence of a Lewis acid or a base. More specifically, if one wants, forexample, a compound wherein n is 3 (i.e., a polypropylene oxidesubstituted compound), one can react the aniline with an epoxidecompound of the formula

If one wants a compound wherein n is 2 (i.e., a polyethylene oxidesubstituted compound), one can react the aniline with an epoxidecompound of the formula

The molar ratio of epoxide compound to N-alkyl aniline is such that thedesired number of repeat alkylene oxide units per N-alkyl anilinemolecule is obtained; for example, if it is desired to have a moleculewith an average of about 10 repeat alkylene oxide units (i.e., x=10),the molar ratio of epoxide compound to N-alkyl aniline is about 10:1.

The reaction can take place in the presence of a catalyst which iseither a base, such as potassium hydroxide or the like, or a Lewis acid,such as BF₃ etherate or the like. The catalyst is present in any desiredor effective amount, in one embodiment at least about 0.01 mole ofcatalyst per every one mole of aniline, in another embodiment at leastabout 0.05 mole of catalyst per every one mole of aniline, and in yetanother embodiment at least about 0.1 mole of catalyst per every onemole of aniline, and in one embodiment no more than about 0.3 mole ofcatalyst per every one mole of aniline, in another embodiment no morethan about 0.2 mole of catalyst per every one mole of aniline, and inyet another embodiment no more than about 0.1 mole of catalyst per everyone mole of aniline, although the relative amounts can be outside ofthese ranges.

Further information regarding these kinds of reactions is disclosed in,for example, Preparation 1 of U.S. Pat. No. 4,091,034, Example 1 of U.S.Pat. No. 4,167,510, Example 1 of U.S. Pat. No. 4,400,320, and Example 1Aof U.S. Pat. No. 5,290,921, the disclosures of each of which are totallyincorporated herein by reference.

Materials of the formula

are also commercially available. For example, a material of this formulawherein n is 2 and x is 10 is available from, for example, HenkelCorporation, Mauldin, S.C. From the same company is also available asSO-7864 a similar material wherein both ethylene oxide and propyleneoxide groups are randomly distributed through the polyalkylene oxidechain in an average molar ratio of about 3.5 moles of ethylene oxidegroups to 6.5 moles of propylene oxide groups.

The azo colorants of the present invention are of the general formula

wherein R, n, and x are as defined hereinabove, and R′ is an aromatic-or heteroaromatic-containing group. R′ can be any aromatic-containing orheteroaromatic-containing group suitable for azo colorants. R′ can be anaryl group (including unsubstituted and substituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the arylgroup), in one embodiment with at least about 2 carbon atoms, and inanother embodiment with at least about 4 carbon atoms, and in oneembodiment with no more than about 60 carbon atoms, and in anotherembodiment with no more than about 50 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including unsubstituted and substituted arylalkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the arylalkyl group), in one embodimentwith at least about 3 carbon atoms, in another embodiment with at leastabout 5 carbon atoms, and in yet another embodiment with at least about7 carbon atoms, and in one embodiment with no more than about 60 carbonatoms, in another embodiment with no more than about 50 carbon atoms,and in yet another embodiment with no more than about 18 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, or an alkylaryl group (including unsubstitutedand substituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, and the like either mayor may not be present in either or both of the alkyl portion and thearyl portion of the alkylaryl group), in one embodiment with at leastabout 3 carbon atoms, in another embodiment with at least about 5 carbonatoms, and in yet another embodiment with at least about 7 carbon atoms,and in one embodiment with no more than about 60 carbon atoms, inanother embodiment with no more than about 50 carbon atoms, and in yetanother embodiment with no more than about 18 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyl orthe like, and wherein the substituents on the substituted aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) thoseindicated hereinabove as suitable for the R group.

Examples of R′ groups include (but are not limited to) thiophenederivatives, benzothiazole derivatives, benzoisothiazole derivatives,thiadiazole derivatives, benzene derivatives, imidazole derivatives, andthe like.

Specific examples of classes of R′ groups include (but are not limitedto) (a) those of the formula

wherein A, G, and J each, independently of the others, is a carbon atomor a hetero atom, such as nitrogen, oxygen, sulfur, phosphorus, silicon,or the like, and R₁, R₂, and R₃ each, independently of the other, is ahydrogen atom, a halogen atom, such as fluorine, chlorine, bromine, oriodine, a cyano group, an alkyl group (including linear, branched,saturated, unsaturated, cyclic, and unsubstituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), in one embodiment with at least 1 carbon atom, and in oneembodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 18 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an aryl group (includingunsubstituted and substituted aryl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the aryl group), in one embodimentwith at least about 5 carbon atoms, and in another embodiment with atleast about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, and in another embodiment with no more than about18 carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including unsubstituted andsubstituted arylalkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the alkyl portion and the arylportion of the arylalkyl group), in one embodiment with at least about 5carbon atoms, in another embodiment with at least about 6 carbon atoms,and in yet another embodiment with at least about 7 carbon atoms, and inone embodiment with no more than about 50 carbon atoms, and in anotherembodiment with no more than about 18 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an alkylaryl group(including unsubstituted and substituted alkylaryl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the alkylportion and the aryl portion of the alkylaryl group), in one embodimentwith at least about 5 carbon atoms, in another embodiment with at leastabout 6 carbon atoms, and in yet another embodiment with at least about7 carbon atoms, and in one embodiment with no more than about 50 carbonatoms, and in another embodiment with no more than about 18 carbonatoms, although the number of carbon atoms can be outside of theseranges, alkoxy, aryloxy, arylalkyloxy, and alkylaryloxy groups, all ofwhich either may or may not be substituted, wherein the alkyl, aryl,arylalkyl, and alkylaryl portions thereof are as defined hereinabove,sulfonamidoalkyl, sulfonamidoaryl, sulfonamidoarylalkyl,sulfonamidoalkylaryl, sulfonamidodialkyl, sulfonamidodiaryl,sulfonamidodiarylalkyl, and sulfonamidodialkylaryl groups, as well ascombinations thereof, all of which either may or may not be substituted,wherein the alkyl, aryl, arylalkyl, and alkylaryl portions thereof areas defined hereinabove, amidoalkyl, amidoaryl, amidoarylalkyl,amidoalkylaryl, amidodialkyl, amidodiaryl, amidodiarylalkyl,amidodialkylaryl, and amidodiarylalkyl groups, as well as combinationsthereof, all of which either may or may not be substituted, wherein thealkyl, aryl, arylalkyl, and alkylaryl portions thereof are as definedhereinabove, thioalkyl, thioaryl, thioarylalkyl, and thioalkylarylgroups, all of which either may or may not be substituted, wherein thealkyl, aryl, arylalkyl, and alkylaryl portions thereof are as definedhereinabove, ester groups of the formula

wherein R″ can be substituted or unsubstituted alkyl, aryl, arylalkyl,and alkylaryl as defined hereinabove, ketone groups of the formula

wherein R′″ can be substituted or unsubstituted alkyl aryl, arylalkyl,and alkylaryl as defined hereinabove, sulfone groups of the formula—SO₂R″″ wherein R″″ can be substituted or unsubstituted alkyl, aryl,arylalkyl, and alkylaryl as defined hereinabove, and the like, whereinthe substituents on any of the substituted forms of these groups can be(but are not limited to) those indicated hereinabove for the R group;(b) those of the formula

wherein A and G are as defined hereinabove and wherein R₄, R₅, R₆, R₇,R₈, and R₉ are defined as R₁, R₂, and R₃ hereinabove; or (c) those ofthe formula

wherein R₁₀, R₁₁, R₁₂, R₁₃, and R₁₄ are defined as R₁, R₂, and R₃hereinabove; and the like. It is to be understood that the A, G, and Jgroups have valencies appropriate to the selected atom, and that thenumber of “R” groups attached thereto can vary depending on the valencyof the atom. For example, in groups of formula (b), when G is a carbonor silicon atom, two R groups can be attached thereto; when G is anitrogen or phosphorus atom and the molecule is nonionic, one R groupcan be attached thereto; when G is a nitrogen or phosphorus atom and themolecule is cationic, two R groups can be attached thereto accompaniedby a suitable anion; when G is an oxygen or sulfur atom and the moleculeis nonionic, no R groups are attached thereto; and the like.

The material of the formula

can be used as an intermediate material and reacted with a suitablediazonium compound to form an azo colorant, Suitable diazonium compoundshave a diazonium salt group that can react with the intermediatematerial to form azo colorants as follows:

One specific example of a suitable reaction is as follows:

More specifically, a diazonium salt corresponding to the appropriate R′group is first prepared by dissolving or dispersing the correspondingprimary amine R′—NH₂ in a cold mineral acid, typically at ice bathtemperatures, with examples of suitable mineral acids including (but notbeing limited to) hydrochloric, hydrobromic, sulfuric, phosphoric, andthe like, as well as mixtures thereof. If desired, a defoaming agentsuch as 2-ethylhexanol can also be present in the reaction mixture. Theprimary amine in acid is then reacted with an azotizing agent, such assodium nitrite (NaNO₂), nitrosyl sulfuric acid (HO₃SONO), or the like,as well as mixtures thereof, to form the diazonium salt R′—N≡N⁺.Thereafter, the reaction mixture can be neutralized to remove any excessNO⁺ by addition of a NO⁺ scavenger, such as sulfamic acid, urea, or thelike, as well as mixtures thereof. The diazonium salt is then added to asolution containing the material of the formula

in a solvent, such as water, other polar solvents, or the like, as wellas mixtures thereof, typically at ice bath temperatures, to form the azocolorant.

Colorants of the present invention can be reacted with various atoms,groups of atoms, monomers, oligomers, or polymers to form variouscolored monomers, oligomers, or polymers having covalently bondedthereto a colorant according to the present invention. Anotherembodiment of the present invention is directed to a compound comprisingtwo or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said moieties each contain no —OH groups, —SHgroups, or primary or secondary amino groups, said moieties being linkedby a central atom or group of atoms or bonded to a polymer.

Examples of colored groups of atoms, monomers, oligomers, or polymerswhich can be prepared with the colorants of the present inventioninclude urethane isocyanate-derived monomers, oligomers, or polymers,urea isocyanate-derived monomers, oligomers, or polymers, urethane/ureaisocyanate-derived monomers, oligomers, or polymers, anhydride monomers,oligomers, or polymers, such as styrene-maleic anhydride monomers,oligomers, or polymers, ester/polyester monomers, oligomers, orpolymers, carbonate/polycarbonate monomers, oligomers, or polymers, andthe like. Colored urethane isocyanate-derived monomers, oligomers, orpolymers, urea isocyanate-derived monomers, oligomers, or polymers, andurethane/urea isocyanate-derived monomers, oligomers, or polymers havingcovalently bonded thereto a colorant according to the present inventionare generally the reaction product of a colorant according to thepresent invention and an isocyanate. Colored urethane isocyanate-derivedmonomers, oligomers, or polymers, urea isocyanate-derived monomers,oligomers, or polymers, and urethane/urea isocyanate-derived monomers,oligomers, or polymers having covalently bonded thereto a colorantaccording to the present invention can be prepared by, for example,processes such as those disclosed in U.S. Pat. No. 5,919,839; U.S. Pat.No. 3,994,835; U.S. Pat. No. 4,132,840; U.S. Pat. No. 4,751,254; U.S.Pat. No. 5,290,921; U.S. Pat. No. 5,270,363; U.S. Pat. No. 4,912,203;U.S. Pat. No. 4,846,846; U.S. Pat. No. 4,507,407; U.S. Pat. No.4,284,729; U.S. Pat. No. 5,864,002; PCT patent application WO 97/13816;J. H. Saunders and K. C. Frisch's “Polyurethanes Part I, Chemistry”published by Interscience of New York, N.Y. in 1962; and Olin Chemicals′Luxate® IM isophorone diisocyanate technical product information sheet;the disclosures of each of which are totally incorporated herein byreference. Further information on isocyanate-derived resins is disclosedin, for example, U.S. Pat. No. 5,782,966; U.S. Pat. No. 5,750,604; U.S.Pat. No. 5,827,918; U.S. Pat. No. 5,830,942; U.S. Pat. No. 5,994,453;U.S. Pat. No. 6,180,692; U.S. Pat. No. 6,018,005; U.S. Pat. No.6,028,138; U.S. Pat. No. 6,048,925; U.S. Pat. No. 6,057,399; and U.S.Pat. No. 5,783,658; the disclosures of each of which are totallyincorporated herein by reference.

For example, a monoisocyanate reacts with an alcohol to form a urethaneas follows:

Diisocyanates react similarly; for example, isophorone diisocyanatereacts with two moles of alcohol to form a diurethane as follows:

Monomeric, oligomeric, and polymeric materials can be prepared whenHO—R_(b) is a colorant according to the present invention.

Examples of suitable isocyanates include monoisocyanates, diisocyanates,triisocyanates, copolymers of a diisocyanate, copolymers of atriisocyanate, polyisocyanates (having more than three isocyanatefunctional groups), and the like, as well as mixtures thereof. Examplesof monoisocyanates include octadecylisocyanate; hexadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and para-tolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like, as well as mixtures thereof.Examples of diisocyanates include isophorone diisocyanate (IPDI);toluene diisocyanate CTDI); diphenylmethane-4,4′-diisocyanate (MDI);hydrogenated diphenylmethane-4,4′-diisocyanate (H12MDI), tetra-methylxylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate: 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; dimer diisocyanate and cyclohexylenediisocyanate and its isomers; uretidione dimers of HDI; and the like, aswell as mixtures thereof. Examples of triisocyanates or theirequivalents include the trimethylolpropane trimer of TDI, and the like,isocyanurate trimers of TDI, HDI, IPDI, and the like, and biuret trimersof TDI, HDI, IPDI, and the like, as well as mixtures thereof. Examplesof higher isocyanate functionalities include copolymers of TDI/HDI, andthe like, and MDI oligomers, as well as mixtures thereof.

Any suitable reaction condition for making urethane compounds bycondensing alcohols with isocyanates can be used to prepare polymericcolorants according to the present invention. Typically (although notnecessarily), the reaction is carried out at elevated temperatures (forexample, from about 60 to about 160° C.) in the presence of an optionalurethane reaction catalyst, such as dibutyl tindilaurate, bismuthtris-neodecanoate, cobalt benzoate, lithium acetate, stannous octoate,triethylamine, or the like, In a specific embodiment, the reactionconditions are conducted in an inert atmosphere, such as argon ornitrogen gas or other suitable gases, to prevent oxidizing or yellowingof the reaction products and to prevent undesirable side reactions, Thereaction can employ an inert solvent, such as toluene or the like, orcan be performed neat (i.e., without a solvent). The mole ratio ofreactants is adjusted so that the isocyanate functionalities arecompletely consumed in the reaction with a slight molar excess ofalcohol-substituted or amine-substituted antioxidant typicallyremaining. The reactants can be added together in any order and/or addedto the reaction as physical mixtures. See, for example, J. H. Saundersand K. C. Frisch's “Polyurethanes Part I, Chemistry” published byInterscience of New York, N.Y. in 1962 and Olin Chemicals' LUXATE® IMisophorone diisocyanate technical product information sheet, thedisclosures of each of which are totally incorporated herein byreference, which provide further explanation of this chemistry.

Colored anhydride resins having covalently bonded thereto a colorantaccording to the present invention are generally the reaction product ofa monomeric colorant according to the present invention and ananhydride. Colored anhydride resins having covalently bonded thereto acolorant according to the present invention can be prepared as disclosedin, for example, U.S. Pat. No. 6,110,264 and U.S. Pat. No. 6,322,624,the disclosures of each of which are totally incorporated herein byreference. Examples of suitable anhydrides include cyclic anhydrides,such as alkylsuccinic anhydrides, alkenylsuccinic anhydrides, and thelike, as well as mixtures thereof. Specific examples include (but arenot limited to) maleic anhydride, 2,3-diphenylmaleic anhydride,trimellitic anhydride, 2-phenylglutaric anhydride, homophthalicanhydride, isatoic anhydride, n-methylisatoic anhydride, 5-chloroisatoicanhydride, phthalic anhydride, 3,3′,4,4′-benzophenone tetracarboxylicdianhydride, 4-methylphthalic anhydride,4,4′-(hexafluoroisopropylidine)-diphthalic anhydride,3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,tetrachlorophthalic anhydride, tetrabromophthalic anhydride,3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,3-nitrophthalic anhydride, 4-nitrophthalic anhydride,1,2,4,5-benzenetetracarboxylic dianhydride, diphenic anhydride,1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic anhydride,4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride,3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride,4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride dipotassiumsalt, 1,4,5,8-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylic dianhydride,cis-1,2,3,6-tetrahydrophthalic anhydride,cis-5-norbornene-endo-2,3dicarboxylic anhydride,endo-bicyco[2,2,2]oct-5-ene-2,3dicarboxylic anhydride, cantharidin,methyl-5-norbornene-2,3-dicarboxylic anhydride,exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, citraconicanhydride, 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylicanhydride, 3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,dichloromaleic anhydride,1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric anhydride,2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride,3-ethyl-3-methylglutaric anhydride, 3,3tetramethyleneglutaric anhydride,hexafluoroglutaric anhydride, 3,5-diacetyltetrahydropyran-2,4,6-trione,ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaaceticdianhydride, diglycolic anhydride, succinic anhydride, methylsuccinicanhydride, 2,2-dimethylsuccinic anhydride, isobuteneylsuccinicanhydride, 2-octen-1-ylsuccinic anhydride, octadecenylsuccinicanhydride, 3-oxabicyclo (3,1,0) hexane-2,4-dione,cis-1,2-cyclohexanedicarboxylic anhydride,trans-1,2-cyclohexanedicarboxylic anhydride, hexahydro-4-methylphthalicanhydride, itaconic anhydride, 2-dodecen-1-ylsuccinic anhydride, and thelike, as well as mixtures thereof, For example, colored styrene-maleicanhydride resins having covalently bonded thereto a colorant accordingto the present invention are generally the reaction product of amonomeric colorant according to the present invention and styrene-maleicanhydride. Copolymers of anhydrides with styrene, butadiene,methoxyvinylether, ethylene, alpha-olefins, mixtures thereof, and thelike, are all suitable examples of polymeric materials with which themonomeric colorants of the present invention can be reacted to formcolored polymeric materials. Specific examples of suitable copolymersinclude (but are not limited to) poly(methyl vinyl ether-maleic acid),poly(acrylic acid-co-maleic acid), poly(vinylchloride-co-vinyl-acetate-co-maleic acid), poly(ethylene-maleicanhydride), poly(maleic anhydride-1-octadecene), poly(styrene-co-maleicanhydride), poly(methyl vinyl ether-maleic anhydride),poly(ethylene-co-ethyl acrylate-co-maleic anhydride),poly(ethylene-co-vinyl acetate)-graft-maleic anhydride,polyethylene-graft-maleic anhydride, polypropylene-graft-maleicanhydride, and the like, as well as mixtures thereof.

The monomeric colorant compounds of the present invention, i.e., thosecontaining only one moiety of the formula

have no more than one —OH, —SH, or —NHR_(b) group per molecule, whereinR_(b) is a hydrogen atom, an alkyl group, an aryl group, an arylalkylgroup, or an alkylaryl group. By this it is meant that, for example, ifthe molecule has one —OH group, it has no —SH groups, no —NHR_(b)groups, and no additional —OH groups. Because the colorant compounds ofthe present invention have one and only one of these groups, in someembodiments of the invention various advantages can be achieved. Forexample, when these colorants are reacted with other materials to formcolored resins, there is no formation of products of undesirably highmolecular weight and no undesired crosslinking. Some advantages areparticularly desirable for phase change ink applications. For example,when these colorants are reacted with other materials to form coloredresins and when these colored resins are incorporated into a phasechange ink, precipitation of the colorant from the ink is reduced; morespecifically, when multifunctional colorants, rather that the chainterminating colorants of the present invention, are employed inreactions of di- or tri-isocyanates and monohydric alcoholic species,some higher molecular weight species are produced which can be insolublein the ink base, often resulting or being manifested as a precipitate inthe prepared material and/or the final ink. In addition, when thesecolorants are reacted with other materials to form colored resins andwhen these colored resins are incorporated into a phase change ink,clogging of printheads and the printer failure accompanying suchclogging can be reduced.

The present invention is also directed to phase change inks. Anotherembodiment of the present invention is directed to a phase change inkcomprising a phase change ink carrier and a colorant compound comprisingone or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein, when the colorant compound contains exactly one ofthe moieties, the moiety contains no more than one —OH, —SH, or primaryor secondary amino group per molecule, and when the colorant compoundcontains more than one of the moieties, said moieties each contain no—OH groups, —SH groups, or primary or secondary amino groups.

In the direct printing mode, the phase change carrier composition in oneembodiment contains one or more materials that enable the phase changeink (1) to be applied in a thin film of uniform thickness on the finalrecording substrate (such as paper, transparency material, and the like)when cooled to ambient temperature after printing directly to therecording substrate, (2) to be ductile while retaining sufficientflexibility so that the applied image on the substrate will not fractureupon bending, and (3) to possess a high degree of lightness, chroma,transparency, and thermal stability.

In an offset printing transfer or indirect printing mode, the phasechange carrier composition in one embodiment exhibits not only thecharacteristics desirable for direct printing mode inks, but alsocertain fluidic and mechanical properties desirable for use in such asystem, as described in, for example, U.S. Pat. No. 5,389,958 thedisclosure of which is totally incorporated herein by reference.

When the phase change ink of the present invention comprises a coloredoligomer or polymer to which colorant molecules of the present inventionare covalently bonded, this colored oligomer or polymer can function asthe sole ink carrier. In addition, such a colored oligomer or polymercan be present in combination with another phase change ink carriercomposition. Further, when the phase change ink of the present inventioncomprises a colorant of the present invention having only one moiety ofthe formula

the colorant is generally present in combination with a phase change inkcarrier composition. Any desired or effective carrier composition can beused. Examples of suitable ink carrier materials include fatty amides,such as monoamides, tetraamides, mixtures thereof, and the like.Specific examples of suitable fatty amide ink carrier materials includestearyl stearamide, a dimer acid based tetra-amide that is the reactionproduct of dimer acid, ethylene diamine, and stearic acid, a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid having at least about 36 carbon atoms,and the like, as well as mixtures thereof. When the fatty amide inkcarrier is a dimer acid based tetra-amide that is the reaction productof dimer acid, ethylene diamine, and a carboxylic acid having at leastabout 36 carbon atoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated,unsaturated, and cyclic alkyl groups, said alkyl group in one embodimenthaving at least about 36 carbon atoms, in another embodiment having atleast about 40 carbon atoms, said alkyl group in one embodiment havingno more than about 200 carbon atoms, in another embodiment having nomore than about 150 carbon atoms, and in yet another embodiment havingno more than about 100 carbon atoms, although the number of carbon atomscan be outside of these ranges. Carboxylic acids of this formula arecommercially available from, for example, Baker Petrolite, Tulsa, Okla.,and can also be prepared as described in Example 1 of U.S. Pat. No.6,174,937, the disclosure of which is totally incorporated herein byreference. Further information on fatty amide carrier materials isdisclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No.4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat.No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S.Pat. No. 6,174,937, and British Patent GB 2238792, the disclosures ofeach of which are totally incorporated herein by reference.

Also suitable as phase change ink carrier materials areisocyanate-derived resins and waxes, such as urethane isocyanate-derivedmaterials, urea isocyanate-derived materials, urethane/ureaisocyanate-derived materials, mixtures thereof, and the like. Furtherinformation on isocyanate-derived carrier materials is disclosed in, forexample, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No.5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat.No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S.Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCTPublication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, andPCT Publication WO 95/04760, the disclosures of each of which aretotally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials canalso be employed as the ink carrier composition for inks of the presentinvention.

Additional suitable phase change ink carrier materials for the presentinvention include paraffins, microcrystalline waxes, polyethylene waxes,ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides andother waxy materials, sulfonamide materials, resinous materials madefrom different natural sources (such as, for example, tall oil rosinsand rosin esters), and many synthetic resins, oligomers, polymers andcopolymers, such as ethylene/vinyl acetate copolymers, ethylene/acrylicacid copolymers, ethylene/vinyl acetate/acrylic acid copolymers,copolymers of acrylic acid with polyamides, and the like, ionomers, andthe like, as well as mixtures thereof. One or more of these materialscan also be employed in a mixture with a fatty amide material and/or anisocyanate-derived material.

In one specific embodiment, the phase change ink carrier comprises theink carrier comprises (a) a polyethylene wax, present in the ink in anamount in one embodiment of at least about 25 percent by weight of theink, in another embodiment of at least about 30 percent by weight of theink, and in yet another embodiment of at least about 37 percent byweight of the ink, and in one embodiment of no more than about 60percent by weight of the ink, in another embodiment of no more thanabout 53 percent by weight of the ink, and in yet another embodiment ofno more than about 48 percent by weight of the ink, although the amountcan be outside of these ranges; (b) a stearyl stearamide wax, present inthe ink in an amount in one embodiment of at least about 8 percent byweight of the ink, in another embodiment of at least about 10 percent byweight of the ink, and in yet another embodiment of at least about 12percent by weight of the ink, and in one embodiment of no more thanabout 32 percent by weight of the ink, in another embodiment of no morethan about 28 percent by weight of the ink, and in yet anotherembodiment of no more than about 25 percent by weight of the ink,although the amount can be outside of these ranges; (c) a dimer acidbased tetra-amide that is the reaction product of dimer acid, ethylenediamine, and a carboxylic acid derivative of a long chain alcohol havinggreater than thirty six carbon atoms, present in the ink in an amount inone embodiment of at least about 10 percent by weight of the ink, inanother embodiment of at least about 13 percent by weight of the ink,and in yet another embodiment of at least about 16 percent by weight ofthe ink, and in one embodiment of no more than about 32 percent byweight of the ink, in another embodiment of no more than about 27percent by weight of the ink, and in yet another embodiment of no morethan about 22 percent by weight of the ink, although the amount can beoutside of these ranges; (d) a urethane resin derived from the reactionof two equivalents of hydroabietyl alcohol and one equivalent ofisophorone diisocyanate, present in the ink in an amount in oneembodiment of at least about 6 percent by weight of the ink, in anotherembodiment of at least about 8 percent by weight of the ink, and in yetanother embodiment of at least about 10 percent by weight of the ink,and in one embodiment of no more than about 16 percent by weight of theink, in another embodiment of no more than about 14 percent by weight ofthe ink, and in yet another embodiment of no more than about 12 percentby weight of the ink, although the amount can be outside of theseranges; (e) a urethane resin that is the adduct of three equivalents ofstearyl isocyanate and a glycerol-based alcohol, present in the ink inan amount in one embodiment of at least about 2 percent by weight of theink, in another embodiment of at least about 3 percent by weight of theink, and in yet another embodiment of at least about 4.5 percent byweight of the ink, and in one embodiment of no more than about 13percent by weight of the ink, in another embodiment of no more thanabout 10 percent by weight of the ink, and in yet another embodiment ofno more than about 7.5 percent by weight of the ink, although the amountcan be outside of these ranges, and (f) an antioxidant, present in theink in an amount in one embodiment of at least about 0.01 percent byweight of the ink, in another embodiment of at least about 0.05 percentby weight of the ink, and in yet another embodiment of at least about0.1 percent by weight of the ink, and in one embodiment of no more thanabout 1 percent by weight of the ink, in another embodiment of no morethan about 0.5 percent by weight of the ink, and in yet anotherembodiment of no more than about 0.3 percent by weight of the ink,although the amount can be outside of these ranges.

The ink carrier is present in the phase change ink of the presentinvention in any desired or effective amount, in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 50 percent by weight of the ink, and in yet anotherembodiment of at least about 90 percent by weight of the ink, and in oneembodiment of no more than about 99 percent by weight of the ink, inanother embodiment of no more than about 98 percent by weight of theink, and in yet another embodiment of no more than about 95 percent byweight of the ink, although the amount can be outside of these ranges.

The phase change inks of the present invention contain a colorantcompound comprising one or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, R′ is an aromatic- or heteroaromatic-containing group,each R_(a), independently of the others, is a halogen atom, an alkylgroup, an alkoxy group, a nitrile group, a nitro group, an amide group,or a sulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is aninteger representing the number of carbon atoms in each repeat alkyleneoxide unit, and x is an integer representing the number of repeatalkylene oxide units, wherein said moieties each contain no —OH groups,—SH groups, or primary or secondary amino groups, said moieties beinglinked by a central atom or group of atoms or bonded to a polymer. Thiscolorant is present in the ink in any desired or effective amount toobtain the desired color or hue, in one embodiment of at least about 1percent by weight of the ink, in another embodiment of at least about 2percent by weight of the ink, and in yet another embodiment of at leastabout 3 percent by weight of the ink, and in one embodiment of no morethan about 20 percent by weight of the ink, in another embodiment of nomore than about 13 percent by weight of the ink, and in yet anotherembodiment of no more than about 6 percent by weight of the ink,although the amount can be outside of these ranges. The colorantaccording to the present invention can either be the sole colorant inthe ink or can be present in combination with other colorants, such asdyes, pigments, mixtures thereof, and the like.

The inks of the present invention can also optionally contain anantioxidant. The optional antioxidants of the ink compositions protectthe images from oxidation and also protect the ink components fromoxidation during the heating portion of the ink preparation process.Specific examples of suitable antioxidants include NAUGUARD® 524,NAUGUARD® 76, and NAUGUARD® 512, commercially available from UniroyalChemical Company, Oxford, Conn., IRGANOX® 1010, commercially availablefrom Ciba Geigy, and the like, When present, the optional antioxidant ispresent in the ink in any desired or effective amount, in one embodimentof at least about 0.01 percent by weight of the ink, in anotherembodiment of at least about 0.1 percent by weight of the ink, and inyet another embodiment of at least about 1 percent by weight of the ink,and in one embodiment of no more than about 20 percent by weight of theink, in another embodiment of no more than about 5 percent by weight ofthe ink, and in yet another embodiment of no more than about 3 percentby weight of the ink, although the amount can be outside of theseranges.

The inks of the present invention can also optionally contain aviscosity modifier. Examples of suitable viscosity modifiers includealiphatic ketones, such as stearone, and the like. When present, theoptional viscosity modifier is present in the ink in any desired oreffective amount, in one embodiment of at least about 0.1 percent byweight of the ink, in another embodiment of at least about 1 percent byweight of the ink, and in yet another embodiment of at least about 10percent by weight of the ink, and in one embodiment of no more thanabout 99 percent by weight of the ink, in another embodiment of no morethan about 30 percent by weight of the ink, and in yet anotherembodiment of no more than about 15 percent by weight of the ink,although the amount can be outside of these ranges.

Other optional additives to the inks include clarifiers, such as UNIONCAMP® X37-523-235 (commercially available from Union Camp), in an amountin one embodiment of at least about 0.01 percent by weight of the ink,in another embodiment of at least about 0.1 percent by weight of theink, and in yet another embodiment of at least about 5 percent by weightof the ink, and in one embodiment of no more than about 98 percent byweight of the ink, in another embodiment of no more than about 50percent by weight of the ink, and in yet another embodiment of no morethan about 10 percent by weight of the ink, although the amount can beoutside of these ranges, tackifiers, such as FORAL® 85, a glycerol esterof hydrogenated abietic (rosin) acid (commercially available fromHercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin)acid (commercially available from Hercules), CELLOLYN® 21, ahydroabietic (rosin) alcohol ester of phthalic acid (commerciallyavailable from Hercules), ARAKAWA KE-311 Resin, a triglyceride ofhydrogenated abietic (rosin) acid (commercially available from ArakawaChemical Industries, Ltd.), synthetic polyterpene resins such as NEVTAC®2300, NEVTACO 100, and NEVTAC® 80 (commercially available from NevilleChemical Company), WINGTACK® 86, a modified synthetic polyterpene resin(commercially available from Goodyear), and the like, in an amount inone embodiment of at least about 0.1 percent by weight of the ink, inanother embodiment of at least about 5 percent by weight of the ink, andin yet another embodiment of at least about 10 percent by weight of theink, and in one embodiment of no more than about 98 percent by weight ofthe ink, in another embodiment of no more than about 75 percent byweight of the ink, and in yet another embodiment of no more than about50 percent by weight of the ink, although the amount can be outside ofthese range, adhesives, such as VERSAMID® 757, 759, or 744 (commerciallyavailable from Henkel), in an amount in one embodiment of at least about0.1 percent by weight of the ink, in another embodiment of at leastabout 1 percent by weight of the ink, and in yet another embodiment ofat least about 5 percent by weight of the ink, and in one embodiment ofno more than about 98 percent by weight of the ink, in anotherembodiment of no more than about 50 percent by weight of the ink, and inyet another embodiment of no more than about 10 percent by weight of theink, although the amount can be outside of these ranges, plasticizers,such as UNIPLEX® 250 (commercially available from Uniplex), thephthalate ester plasticizers commercially available from Monsanto underthe trade name SANTICIZER®, such as dioctyl phthalate, diundecylphthalate, alkylbenzyl phthalate (SANTICIZER® 278), triphenyl phosphate(commercially available from Monsanto), KP-140®, a tributoxyethylphosphate (commercially available from FMC Corporation), MORFLEX® 150, adicyclohexyl phthalate (commercially available from Morflex ChemicalCompany Inc.), trioctyl trimellitate (commercially available fromEastman Kodak Co.), and the like, in an amount in one embodiment of atleast about 0.1 percent by weight of the ink, in another embodiment ofat least about 1 percent by weight of the ink, and in yet anotherembodiment of at least about 2 percent by weight of the ink, and in oneembodiment of no more than about 50 percent by weight of the ink, inanother embodiment of no more than about 30 percent by weight of theink, and in yet another embodiment of no more than about 10 percent byweight of the ink, although the amount can be outside of these ranges,and the like.

The ink compositions of the present invention in one embodiment havemelting points of no lower than about 50° C., in another embodiment ofno lower than about 70° C., and in yet another embodiment of no lowerthan about 80° C., and have melting points in one embodiment of nohigher than about 160° C., in another embodiment of no higher than about140° C., and in yet another embodiment of no higher than about 100° C.,although the melting point can be outside of these ranges.

The ink compositions of the present invention generally have meltviscosities at the jetting temperature (in one embodiment no lower thanabout 75° C., in another embodiment no lower than about 100° C., and inyet another embodiment no lower than about 120° C., and in oneembodiment no higher than about 180° C., and in another embodiment nohigher than about 150° C., although the jetting temperature can beoutside of these ranges) in one embodiment of no more than about 30centipoise, in another embodiment of no more than about 20 centipoise,and in yet another embodiment of no more than about 15 centipoise, andin one embodiment of no less than about 2 centipoise, in anotherembodiment of no less than about 5 centipoise, and in yet anotherembodiment of no less than about 7 centipoise, although the meltviscosity can be outside of these ranges.

The ink compositions of the present invention can be prepared by anydesired or suitable method. For example, the ink ingredients can bemixed together, followed by heating, to a temperature in one embodimentof at least about 100° C., and in one embodiment of no more than about140° C., although the temperature can be outside of these ranges, andstirring until a homogeneous ink composition is obtained, followed bycooling the ink to ambient temperature (typically from about 20 to about25° C.). The inks of the present invention are solid at ambienttemperature.

The inks of the present invention can be employed in apparatus fordirect printing ink jet processes and in indirect (offset) printing inkjet applications. Another embodiment of the present invention isdirected to a process which comprises incorporating an ink of thepresent invention into an ink jet printing apparatus, melting the ink,and causing droplets of the melted ink to be ejected in an imagewisepattern onto a recording substrate. A direct printing process is alsodisclosed in, for example, U.S. Pat. No. 5,195,430, the disclosure ofwhich is totally incorporated herein by reference. Yet anotherembodiment of the present invention is directed to a process whichcomprises incorporating an ink of the present invention into an ink jetprinting apparatus, melting the ink, causing droplets of the melted inkto be ejected in an imagewise pattern onto an intermediate transfermember, and transferring the ink in the imagewise pattern from theintermediate transfer member to a final recording substrate. In aspecific embodiment thereof, the intermediate transfer member is heatedto a temperature above that of the final recording sheet and below thatof the melted ink in the printing apparatus. An offset or indirectprinting process is also disclosed in, for example, U.S. Pat. No.5,389,958, the disclosure of which is totally incorporated herein byreference. In one specific embodiment, the printing apparatus employs apiezoelectric printing process wherein droplets of the ink are caused tobe ejected in imagewise pattern by oscillations of piezoelectricvibrating elements. Inks of the present invention can also be employedin other hot melt printing processes, such as hot melt acoustic ink jetprinting, hot melt thermal ink jet printing, hot melt continuous streamor deflection ink jet printing, and the like. Phase change inks of thepresent invention can also be used in printing processes other than hotmelt ink jet printing processes.

Any suitable substrate or recording sheet can be employed, includingplain papers such as XEROX® 4024 papers, XEROX® Image Series papers,Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coatedpapers such as Sharp Company silica coated paper, JuJo paper, HammermillLaserprint Paper, and the like, transparency materials, fabrics, textileproducts, plastics, polymeric films, inorganic substrates such as metalsand wood, and the like.

Specific embodiments of the invention will now be described in detail.These examples are intended to be illustrative, and the invention is notlimited to the materials, conditions, or process parameters set forth inthese embodiments. All parts and percentages are by weight unlessotherwise indicated.

Example I Phase Separation of N-Ethyl Aniline Ethoxylate

To a 100 milliliter beaker equipped with a magnetic stirrer was addedabout 50 milliliters of POE(10) N-ethyl aniline, of the formula

(obtained from Henkel Corp, Mauldin, S.C.) and about 65 milliliters ofdeionized water. The mixture was placed on a magnetic stirring hot plateand stirring and heating were initiated. When the temperature reached90° C., the beaker was removed from heat and stirring and was allowed tocool slowly. After several minutes, separation of layers began to occur,and after about 2 hours, the temperature had returned to roomtemperature and the separation was complete. A separation of the twolayers was visually observed, and separation of the layers was performedwith a separatory funnel.

Colorant Preparation

To a 500 milliliter 3-necked kettle equipped with a thermometer, Truborestirrer, and constant pressure addition funnel was added about 115 gramsof 85 percent H₃PO₄ (obtained from Olin Corp., Norwalk, Conn.) in water,about 31 grams of 95 percent H₂SO₄ (obtained from Olin Corp., Norwalk,Conn.) in water, and 2 drops of 2-ethylhexanol (obtained from AldrichChemical Co., Milwaukee, Wis.). Stirring was then initiated and thekettle was placed in a salt/ice bath to cool the mixture to about 0° C.Once 0° C. was reached, 10.2 grams of 2-amino-4-methylbenzothiazole(obtained from Aldrich Chemical Co.) was added with stirring and thetemperature was maintained at 0° C. To the constant pressure additionfunnel was then added about 21.7 grams of nitrosyl sulfuric acid(obtained from Aldrich Chemical Co.) in a dropwise fashion, maintainingthe temperature at about 0° C., over a period of about 1.5 hours. Thereaction mixture was subsequently maintained at 0° C. with stirring foran additional 1.5 hours to ensure complete diazotization. Thereafter,about 0.7 gram of sulfamic acid (obtained from Aldrich Chemical Co.) wasadded with stirring to neutralize any excess NO⁺. The diazo mixture wasthen slowly added over about 0.75 hour to a 1 liter beaker equipped witha stir magnet in a 5° C. ice bath, the beaker containing about 36.0grams of the POE(10) N-ethyl aniline purified as indicated above, 150milliliters of deionized water, and about 2.0 grams of urea (obtainedfrom Aldrich Chemical Co.). The diazo colorant was allowed to stir coolfor about 2 hours, followed by stirring at room temperature overnight.The diazo colorant was then neutralized to a pH of about 7 with a 50percent aqueous solution of sodium hydroxide (solid material obtainedfrom Aldrich Chemical Co.), keeping the temperature below about 60° C.Following neutralization, the colorant was poured into a 1 literseparatory funnel and allowed to phase separate. The bottom salt/waterlayer was discarded and the liquid colored product layer was dissolvedin methylene chloride (obtained from Aldrich Chemical Co.) and runthrough a small “plug” of silica gel (70-230 mesh, for columnchromatography, obtained from Aldrich Chemical Co.) to remove any polarimpurities. The methylene chloride layer was then collected and themethylene chloride removed via rotary evaporation, yielding a viscousred liquid. The resulting colorant is expected to have an absorptionmaxima consistent with the following structure:

Example II

To a 500 milliliter 3-necked kettle equipped with a thermometer, Truborestirrer, and constant pressure addition funnel was added about 27.0grams of deionized water, about 20 grams of 95 percent H₂SO₄ (obtainedfrom Olin Corp., Norwalk, Conn.) in water, and 2 drops of 2-ethylhexanol(obtained from Aldrich Chemical Co., Milwaukee, Wis.). Stirring was theninitiated and the kettle was placed in a salt/ice bath to cool themixture to about 0° C. Once 0° C. was reached, 10.3 grams of2-chloro-4-(methylsulfone) aniline (CAMSU, obtained from Clariant Corp.,Charlotte, N.C.) was added with stirring and the temperature wasmaintained at 0° C. To the constant pressure addition funnel was thenadded about 21.0 grams of nitrosyl sulfuric acid (obtained from AldrichChemical Co.) in a dropwise fashion, maintaining the temperature atabout 0° C., over a period of about 1.5 hours. The reaction mixture wassubsequently maintained at 0° C. with stirring for an additional 1.5hours to ensure complete diazotization. Thereafter, about 1.0 gram ofsulfamic acid (obtained from Aldrich Chemical Co.) was added withstirring to neutralize any excess NO⁺. The diazo mixture was then slowlyadded over about 0.75 hour to a 1 liter beaker equipped with a stirmagnet in a 5° C. ice bath, the beaker containing about 29.1 grams ofthe POE(10) N-ethyl aniline purified as indicated in Example I, 150milliliters of deionized water, and about 2.0 grams of urea (obtainedfrom Aldrich Chemical Co.). The diazo colorant was allowed to stir coolfor about 2 hours, followed by stirring at room temperature overnight.The diazo colorant was then neutralized to a pH of about 7 with a 50percent aqueous solution of sodium hydroxide (solid material obtainedfrom Aldrich Chemical Co.), keeping the temperature below about 60° C.Following neutralization, the colorant was poured into a 1 literseparatory funnel and allowed to phase separate. The bottom salt/waterlayer was discarded and the liquid colored product layer was dissolvedin methylene chloride (obtained from Aldrich Chemical Co.) and runthrough a small “plug” of silica gel (70-230 mesh, for columnchromatography, obtained from Aldrich Chemical Co.) to remove any polarimpurities. The methylene chloride layer was then collected and themethylene chloride removed via rotary evaporation, yielding a viscousorange liquid. The resulting colorant was consistent with the followingformula:

Example III

The process of Example I is repeated except that a random POE (3.5) POP(6.5) N-ethyl aniline, of the formula

wherein 3.5 represents the average number of repeat polyoxyethyleneunits per molecule and 6.5 represents the average number of repeatpolyoxypropylene units per molecule, and wherein the polyoxyethylene andpolyoxypropylene units are randomly mixed within the polyoxyalkylenechain (available as SO-7864 from Henkel Corp., Mauldin, S.C.) issubstituted for the POE(10) N-ethyl aniline. It is believed that acolorant consistent with the formula

will be obtained.

Example IV

The process of Example II is repeated except that a random POE (3.5) POP(6.5) N-ethyl aniline, of the formula

wherein 3.5 represents the average number of repeat polyoxyethyleneunits per molecule and 6.5 represents the average number of repeatpolyoxypropylene units per molecule, and wherein the polyoxyethylene andpolyoxypropylene units are randomly mixed within the polyoxyalkylenechain (available as SO-7864 from Henkel Corp., Mauldin, S.C.) issubstituted for the POE(10) N-ethyl aniline. It is believed that acolorant of the formula

will be obtained.

Example V Reaction Product of Benzophenonetetracarboxylic Dianhydride,Octophenol Ethoxylate, and Red Azo Monohydroxyl Polyoxyalkylene Colorant

To a 1,000 milliliter three-neck resin kettle equipped with a Truborestirrer, N₂ inlet, and thermocouple-temperature controller is added150.0 grams (0.93 equivalents) of benzophenonetetracarboxylicdianhydride (available from Aldrich Chemical Co., Milwaukee, Wis.) and211.6 grams (0.83 equivalents) of IGEPALO CA-210 (octylphenolethoxylate, available from Rhone-Poulenc Co., Cranbury, N.J. Note:TRITON® X15 octylphenol ethoxylate, available from Union CarbideChemicals and Plastics Company Inc., Danbury, Conn., can be directlysubstituted for IGEPAL® CA-210 in this reaction). The reaction mixtureis heated to 150° C. with stirring under nitrogen. After 1.0 hours at150° C., the temperature is increased to 170° C. and held at thattemperature for 3.5 hours. A red azo monohydroxyl polyoxyalkylenecolorant (74.3 grams; 0.098 equivalents) corresponding to the colorantprepared in Example I is then added and allowed to react for 3 hours.The final red colored resin product is then poured into aluminum moldsand allowed to cool and harden.

Example VI

The colored resin prepared in Example V (20.5 grams) is combined with58.7 grams of stearyl stearamide wax (KEMAMIDE® S-180, available fromCrompton Corporation, Greenwich, Conn.), 20.5 grams of glycerol ester ofhydrogenated abietic (rosin) acid (KE-100, available from ArakawaChemical Industries, Ltd.), and 0.2 gram of NAUGUARD® 445 antioxidant(available from Uniroyal Chemical Co., Middlebury, Conn.). Theingredients are heated to 115° C. until molten, mixed, filtered througha disc filter, poured into sticks, and used to generate prints in aXEROX® PHASER 860 printer.

Example VII Reaction Product of Octylphenol Ethoxylate, IsophoroneDiisocyanate, and Red Azo Monohydroxyl Polyoxyalkylene Colorant

525.0 grams (4.73 equivalents) of isophorone diisocyanate (DESMODUR I;isophorone diisocyanate, available from Bayer Corp., Pittsburgh, Pa.)and 1.5 grams of dibutyltindilaurate catalyst (available from AldrichChemical Co., Milwaukee, Wis.), followed by 1,150 grams (4.52equivalents) of octylphenol ethoxylate (IGEPAL CA-210, octylphenolethoxylate, available from Rhone-Poulenc Co., Cranbury, N.J.), are addedto a 3,000 milliliter three-neck resin kettle equipped with a Truborestirrer, N₂ atmosphere inlet, and a thermocouple-temperature controller.The reaction mixture is heated to about 135° C. with stirring undernitrogen. After 2.0 hours at about 135° C., 156 grams (0.210equivalents) of a red azo monohydroxyl polyoxyalkylene colorant preparedas described in Example I is added and the reaction mixture is heatedfor approximately 2 hours. An additional 110.0 grams (0.433 equivalents)of octylphenol ethoxylate are added and the reaction mixture is heatedat about 150° C. for approximately 2 hours. An FT-IR of the product isobtained to ensure that all of the isocyanate (NCO) functionality hasbeen consumed. The absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies are used to confirm that the isocyanate has been consumed.The diurethane reaction product is then poured into aluminum molds andallowed to cool and harden.

Example VIII

In a stainless steel beaker are combined 500 grams of stearyl stearamidewax (KEMAMIDE® S-180, available from Crompton Corporation, Greenwich,Conn.), 125 grams of UNIREZ 2970 tetra-amide resin (available from UnionCamp, Wayne, N.J.), 208 grams of the colored resin prepared as describedin Example VII, and 1.6 grams of NAUGUARD® 445 antioxidant (availablefrom Uniroyal Chemical Co., Middlebury, Conn.). The materials are meltedtogether at a temperature of about 140° C. in an oven, then blended bystirring in a temperature controlled mantle at about 115° C. for about0.5 hour. After stirring, the resulting ink is filtered through a heatedMott apparatus (available from Mott Metallurgical) using #3 Whatmanfilter paper and a pressure of about 15 psi. The filtered phase changeink is then poured into molds, allowed to solidify to form ink sticks,and used to generate prints in a XEROX® PHASER 860 printer.

Example IX Reaction Product of Styrene-Maleic Anhydride Polymer withNeodol 1-3 and Red Azo Monohydroxyl Polyoxyalkylene Colorant

To a 500 milliliter three-neck resin kettle equipped with a TEFLON®coated magnet, oil bath, and condenser was added 14.0 grams (0.068equivalents) of styrene-maleic anhydride polymer (SMA 1000, availablefrom Atochem Inc., Malvern, Pa.), 15.9 grams (0.052 equivalents) of analcohol of the formula C₁₁H₂₂—O—(CH₂CH₂O)_(n)H wherein n has an averagevalue of 3 (NEODOL 1-3, available from Shell Chemical Company, Houston,Tex.), 12.7 grams (0.017 equivalents) of the red azo monohydroxylpolyoxyalkylene colorant prepared in Example I, about 250 grams ofacetonitrile (available from Aldrich Chemical Co., Milwaukee, Wis.), and2 drops of 1-methylimidazole catalyst (available from Aldrich ChemicalCo.). The reaction mixture was heated with stirring to reflux and heldat that state for 2 days. After 2 days, the acetonitrile was removed bydistillation. The red viscous colored product still in the flask wasthen placed in a vacuum oven to remove any residue of acetonitrile. Thefinal red viscous material had a T_(g) of −38° C.

Example X

To a 100 milliliter beaker equipped with magnetic stir was added about 8grams of the red material prepared as described in Example IX and 35milliliters of concentrated ammonia solution. Stirring was continueduntil all the solid material dissolved. About 2 milliliters of thisaqueous solution was placed on the platen of a K-proofer and prints weremade. The prints were allowed to dry and tested for washfastness. Nobleeding of color was observed.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A compound comprising two or more moieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units and is at least about 2, wherein said moieties each containno —OH groups, —SH groups, or primary or secondary amino groups, saidmoieties being linked by a central atom or group of atoms.
 2. A compoundaccording to claim 1 wherein R is an alkyl group with at least onecarbon atom and with no more than about 50 carbon atoms, an aryl groupwith at least about 5 carbon atoms and with no more than about 50 carbonatoms, an arylalkyl group with at least about 6 carbon atoms and with nomore than about 50 carbon atoms, or an alkylaryl group with at leastabout 6 carbon atoms and with no more than about 50 carbon atoms.
 3. Acompound according to claim 1 wherein R is ethyl.
 4. A compoundaccording to claim 1 wherein R′ is an aryl group, an arylalkyl group, analkylaryl group.
 5. A compound according to claim 1 wherein R′ is anaryl group with at least about 2 carbon atoms and with no more thanabout 60 carbon atoms, an arylalkyl group with at least about 3 carbonatoms and with no more than about 60 carbon atoms, or an alkylaryl groupwith at least about 3 carbon atoms and with no more than about 60 carbonatoms.
 6. A compound according to claim 1 wherein R′ is selected fromthe group consisting of (1) thiophene derivatives of the formula

(2) benzothiazole derivatives of the formula

(3) benzoisothiazole derivatives of the formulae

(4) thiadiazole derivatives of the formulae

(5) benzene derivatives of the formula

and (6) imidazole derivatives of the formula

wherein R₁, R₂, R₃, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, and R₁₄ each,independently of the other, is a hydrogen atom, a halogen atom, a cyanogroup, an alkyl group, an aryl group, an arylalkyl group, an alkylarylgroup, an alkoxy group, an aryloxy group, an arylalkyloxy group, analkylaryloxy group, a sulfonamidoalkyl group, a sulfonamidoaryl group, asulfonamidoarylalkyl group, a sulfonamidoalkylaryl, group, asulfonamidodialkyl group, a sulfonamidodiaryl group, asulfonamidodiarylalkyl group, a sulfonamidodialkylaryl group, anamidoalkyl group, an amidoaryl group, an amidoarylalkyl group, anamidoalkylaryl group, an amidodialkyl group, an amidodiaryl group, anamidodiarylalkyl group, an amidodialkylaryl group, an amidodiarylalkylgroup, a thioalkyl group, a thioaryl group, a thioarylalkyl group, athioalkylaryl group, an ester group of the formula

wherein R″ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, a ketone group of the formula

wherein R′″ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, a sulfone group of the formula —SO₂R″″ wherein R″″ isan alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup.
 7. A compound according to claim 1 wherein R′ is (a) of theformula

wherein A, G, and J each, independently of the others, is a carbon atomor a hetero atom, R₁, R₂, and R₃ each, independently of the other, is ahydrogen atom, a halogen atom, a cyano group, an alkyl group, an arylgroup, an arylalkyl group, an alkylaryl group, an alkoxy group, anaryloxy group, an arylalkyloxy group, an alkylaryloxy group, asulfonamidoalkyl group, a sulfonamidoaryl group, a sulfonamidoarylalkylgroup, a sulfonamidoalkylaryl, group a sulfonamidodialkyl group, asulfonamidodiaryl group, a sulfonamidodiarylalkyl group, asulfonamidodialkylaryl group, an amidoalkyl group, an amidoaryl group,an amidoarylalkyl group, an amidoalkylaryl group, an amidodialkyl group,an amidodiaryl group, an amidodiarylalkyl group, an amidodialkylarylgroup, an amidodiarylalkyl group, a thioalkyl group, a thioaryl group, athioarylalkyl group, a thioalkylaryl group, an ester group of theformula

wherein R″ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, a ketone group of the formula

wherein R′″ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, a sulfone group of the formula —SO₂R″″ wherein R″″ isan alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup; (b) of the formula

wherein R₄, R₅, R₆, R₇, R₈, and R₉ each, independently of the others,can be selected from the same groups as R₁, R₂, and R₃; or (c) those ofthe formula

wherein R₁₀, R₁₁, R₁₂, R₁₃, and R₁₄ each, independently of the others,can be selected from the same groups as R₁, R₂, and R₃.
 8. A compoundaccording to claim 1 wherein R′ is


9. A compound according to claim 1 wherein R′ is


10. A compound according to claim 1 wherein n is at least about 2 andwherein n is no more than about
 18. 11. A compound according to claim 1wherein n is no more than about
 4. 12. A compound according to claim 1wherein x is at least about 2 and wherein x is no more than about 100.13. A compound according to claim 1 wherein x is at least about 5 andwherein x is no more than about
 20. 14. A compound according to claim 1wherein each R_(a), independently of the others, is a fluorine atom, achlorine atom, a bromine atom, an iodine atom, an alkyl group with atleast one carbon atom and with no more than about 25 carbon atoms, analkoxy group with at least one carbon atom and with no more than about25 carbon atoms, a nitrile group, a nitro group, an amide group of theformula

wherein R_(m) is a hydrogen atom, an alkyl group with at least 1 carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast 5 carbon atoms and with no more than about 50 carbon atoms, anarylalkyl group with at least about 6 carbon atoms and with no more thanabout 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms, or asulfonamide group of the formula

wherein R_(p) is a hydrogen atom, an alkyl group with at least 1 carbonatom and with no more than about 50 carbon atoms, an aryl group with atleast 5 carbon atoms and with no more than about 50 carbon atoms, anarylalkyl group with at least about 6 carbon atoms and with no more thanabout 50 carbon atoms, or an alkylaryl group with at least about 6carbon atoms and with no more than about 50 carbon atoms.
 15. A compoundaccording to claim 1 wherein the moieties are linked by a group of atomswhich is derived from an isocyanate.
 16. A compound according to claim15 wherein the isocyanate is a diisocyanate.
 17. A compound according toclaim 16 wherein the diisocyanate is isophorone diisocyanate; toluenediisocyanate; diphenylmethane-4,4′-diisocyanate; hydrogenateddiphenylmethane-4,4′-diisocyanate; tetra-methyl xylene diisocyanate;hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3′-dimethoxy-4,4′-biphenyldiisocyanate;3,3′-dimethyl-4,4′-bimethyl-4,4′-biphenyldiisocyanate; phenylenediisocyanate; 4,4′-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4′-methylenebis(2,6-diethylphenyl isocyanate); 1,12-disocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; cyclohexylene diisocyanate; a uretidione dimerof hexamethylene-1,6-diisocyanate; or mixtures thereof.
 18. A compoundaccording to claim 15 wherein the isocyanate is a triisocyanate.
 19. Acompound according to claim 1 wherein the moieties are linked by a groupof atoms which is a urethane.
 20. A compound comprising two or moremoieties of the formula

wherein R is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, and wherein R can be joined to the phenyl moiety toform a ring, R′ is an aromatic- or heteroaromatic-containing group, eachR_(a), independently of the others, is a halogen atom, an alkyl group,an alkoxy group, a nitrile group, a nitro group, an amide group, or asulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an integerrepresenting the number of carbon atoms in each repeat alkylene oxideunit, and x is an integer representing the number of repeat alkyleneoxide units, wherein said moieties each contain no —OH groups, —SHgroups, or primary or secondary amino groups, said moieties being linkedby a group of atoms which is an anhydride.
 21. A compound according toclaim 20 wherein the anhydride is a cyclic anhydride.
 22. A compoundaccording to claim 20 wherein the anhydride is 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-(hexafluoroisopropylidine)-diphthalicanhydride, 1,2,4,5-benzenetetracarboxylic dianhydride,1,4,5,8-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylicdianhydride,bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylicdianhydride,ethylenediaminetetraacetic dianhydride, diethylenetriaminepentaaceticdianhydride, or mixtures thereof.